U.S. patent application number 10/231554 was filed with the patent office on 2004-03-04 for modified amine for boiler water treatment.
This patent application is currently assigned to JohnsonDiversey, Inc.. Invention is credited to Balow, Sue Ann, Emerson, James, Steimel, Lyle H..
Application Number | 20040040910 10/231554 |
Document ID | / |
Family ID | 31976734 |
Filed Date | 2004-03-04 |
United States Patent
Application |
20040040910 |
Kind Code |
A1 |
Steimel, Lyle H. ; et
al. |
March 4, 2004 |
Modified amine for boiler water treatment
Abstract
The present invention provides a method of treating boiler and
condensate water by the addition of an effective amount of a
hydroxyamine-acid ester treatment reagent or an all-in-one
treatment composition comprising a hydroxyamine-acid ester.
Modification of a hydroxyamine to a hydroxyamine-acid ester
generally reduces the odors of the amine while providing a means to
formulate the composition into a solid form. The ester typically
decomposes at conditions in the boiler to release the hydroxyamine
to treat the boiler water. Other components used to treat boiler
water and condensate related problems may be formulated with the
hydroxyamine-acid ester to form the all-in-one treatment
composition.
Inventors: |
Steimel, Lyle H.; (Forest
Park, OH) ; Emerson, James; (Cincinnati, OH) ;
Balow, Sue Ann; (Maineville, OH) |
Correspondence
Address: |
Gregory J. Lunn, Esq.
Wood, Herron & Evans, L.L.P.
2700 Carew Tower
441 Vine Street
Cincinnati
OH
45202-2917
US
|
Assignee: |
JohnsonDiversey, Inc.
|
Family ID: |
31976734 |
Appl. No.: |
10/231554 |
Filed: |
August 30, 2002 |
Current U.S.
Class: |
210/700 |
Current CPC
Class: |
C02F 2303/08 20130101;
C02F 5/025 20130101; C02F 2103/023 20130101; C02F 1/687 20130101;
C02F 5/12 20130101; C23F 11/08 20130101; C23F 11/16 20130101; C02F
2303/02 20130101; C23F 11/1676 20130101; C23F 11/1673 20130101;
C02F 5/125 20130101 |
Class at
Publication: |
210/700 |
International
Class: |
C02F 001/68 |
Claims
What is claimed is:
1. A boiler water treatment composition comprising: an ester formed
from a hydroxyamine and an acid and having a hydroxyamine to acid
mole ratio in the range of from about 1:1 to about 19:1; and at
least one of an oxygen scavenging agent, an alkalinity control
agent, a hardness reducing agent, and an iron controlling agent, in
amounts effective to treat boiler water.
2. The composition of claim 1 wherein the ester is selected from
the group consisting of a phosphate ester, a phosphonate ester, a
sulfate ester, and a sulfonate ester.
3. The composition of claim 1 wherein the acid is selected from the
group consisting of a phosphonic acid having the general formula
(OR).sub.2--P(O)OH, and a sulfonic acid having the general formula
(OR)S(O).sub.2OH, wherein each R independently is selected from the
group consisting of H, alkyl, cycloalkyl, aryl, and heteroaryl
organic structures having up to 10 atoms selected from the group
consisting of C, N and O.
4. The composition of claim 1 wherein the ester is formed from: a
hydroxyamine having the general formula
HO--(CR.sup.1R.sup.2).sub.n--N--R- .sup.3R.sup.4 wherein R.sup.1,
R.sup.2, R.sup.3, and R.sup.4, at each occurrence, is independently
selected from the group consisting of H, alkyl, cycloalkyl, aryl,
and heteroaryl organic structures having up to 10 atoms selected
from the group consisting of C, N, and O, and wherein R.sup.3 and
R.sup.4 taken together with the nitrogen to which they are attached
can form a 5 or 6 membered ring containing 0-2 additional
heteroatoms selected from N or O, and wherein R.sup.1 or R.sup.2,
independently, can be attached to R.sup.3 or R.sup.4,
independently, to form a 5 or 6 membered ring containing 0-2
additional heteroatoms selected from N or 0, and n is an integer
from 0-10; and an acid selected from the group consisting of
polyphosphoric acid, aminotri(methylene phosphonic acid),
1-hydroxyethylidene-1,1-diphosphonic acid, and 1,2,4-tricarboxylic
acid-butane-2-phosphonic acid.
5. The composition of claim 1 wherein the hydroxyamine is selected
from the group consisting of hydroxy-modified cyclohexylamine,
hydroxy-modified morpholine, hydroxy-modified octadecylamine,
N,N-diethylethanolamine, 2-amino-2-methyl-1-propanol,
1,1-dimethylaminepropanol, 2-dimethylamino-2-methyl-1-propanol,
hydroxy-modified N,N-dimethyl-1,3-propanediamine, and ammonium
hydroxide.
6. The composition of claim 1 wherein the ester is present in at
least 0.15% by weight of the composition.
7. The composition of claim 1 wherein the oxygen scavenging agent
is selected from the group consisting of sulfite and polyhydroxy
acid.
8. The composition of claim 1 wherein the alkalinity control agent
is selected from the group consisting of carbonate, hydroxide and
amine.
9. The composition of claim 1 wherein the hardness reducing agent
is selected from the group consisting of carbonate, polyacrylic
acid, polymethacrylic acid, and salts thereof, and polymaleate.
10. The composition of claim 1 wherein the iron controlling agent
is a glucoheptonate.
11. The composition of claim 7 wherein the sulfite is selected from
the group consisting of sodium sulfite and potassium sulfite; and
the polyhydroxy acid is selected from the group consisting of
ascorbic acid and erythorbic acid.
12. The composition of claim 4 wherein the composition is a
solid.
13. The composition of claim 1 wherein the hydroxyamine is N,
N-diethylethanolamine present in about 0.1% to about 30% by weight
of the composition
14. The composition of claim 1 wherein the ester is
N,N-diethylaminoethanol-1-hydroxyethylene-1-phosphono-1-phosphonate
ester present in about 0.1% to about 50% by weight of the
composition.
15. A boiler water treatment composition comprising:
Glucoheptonate: 0% to 2.0%; Sulfite: 0.1% to 60%; Polyhydroxy acid:
0.1% to 5.0%; an ester: 0.01% to 50%; a polymer: 0.1% to 10%;
Polymaleate: 0.1% to 10%; Carbonate: 0.0% to 20%; Water soluble
base: 0.0% to 40.0%, wherein the sulfite is selected from the group
consisting of sodium sulfite and potassium sulfite; the polyhydroxy
acid is selected from the group consisting of ascorbic acid and
erythorbic acid; the ester is formed from a hydroxyamine and a
phosphonic acid, wherein the hydroxyamine is selected from the
group consisting of hydroxy-modified cyclohexylamine,
hydroxy-modified morpholine, hydroxy-modified octadecylamine,
N,N-diethylethanolamine, 2-amino-2-methyl-1-propanol,
1,1-dimethylamine-propanol, 2-dimethylamino-2-methyl-1-propanol,
hydroxy-modified N,N-dimethyl-1,3-propanediamine, and ammonium
hydroxide, and the phosphonic acid is selected from the group
consisting of aminotri(methylene phosphonic acid),
1-hydroxyethylidene-1,1-diphosphonic acid, and 1,2,4-tricarboxylic
acid-butane-2-phosphonic acid, and wherein the polymer is selected
from the group consisting of polyacrylic acid, polymethacrylic
acid, and salts thereof; the polymaleate is polymaleic acid or the
salt thereof; and the carbonate is sodium carbonate or potassium
carbonate.
16. The composition of claim 15 wherein the hydroxyamine to
phosphonic acid mole ratio is in the range of from about 1:1 to
about 3:1.
17. The composition of claim 15 wherein the hydroxyamine is N,
N-diethylethanolamine present in about 0.1% to about 30% by weight
of the composition.
18. The composition of claim 15 wherein the ester is
N,N-diethylaminoethanol-1-hydroxyethylene-1-phosphono-1-phosphonate
ester present in about 0.1% to about 50% by weight of the
composition.
19. The composition of claim 15 wherein the composition is a
solid.
20. The composition of claim 1 wherein the composition comprises:
Sodium Glucoheptonate: 0.01% to 5.0%; Sodium sulfite: 1.0% to 30%;
Ascorbic acid: 0.1% to 5.0%; Sodium polymethacrylate having a
molecular weight between 500-5000: 1.0% to 10%;
N,N-diethylaminoethanol-1-hydroxyethylene--
1-phosphono-1-phosphonate ester: 0.1% to 50%; Maleic acid having a
molecular weight between 500-1000: 0.1% to 5.0%; Sodium carbonate:
0% to 20%; Sodium hydroxide: 0% to 40%; and Water: to 100%, and the
composition is a dry powder.
21. A method of treating boiler water comprising the addition of:
an ester formed from a hydroxyamine and an acid and having a
hydroxyamine to acid mole ratio in the range of from about 1:1 to
about 19:1 to water in said boiler.
22. The method of claim 21 wherein the ester is a phosphate ester,
phosphonate ester, sulfate ester, or sulfonate ester.
23. The method of claim 21 wherein the acid is a phosphonic acid
having the general formula (OR).sub.2--P(O)OH, or a sulfonic acid
having the general formula (OR)S(O).sub.2OH, wherein R
independently is selected from the group consisting of H, alkyl,
cycloalkyl, aryl, and heteroaryl organic structures having up to 10
atoms selected from the group consisting of C, N, and O.
24. The method claimed in claim 21 wherein the ester is formed
from: a hydroxyamine having the general formula
HO--(CR.sup.1R.sup.2).sub.n--N--R- .sup.3R.sup.4 wherein R.sup.1,
R.sup.2, R.sup.3, and R.sup.4, at each occurrence, is independently
selected from the group consisting of H, alkyl, cycloalkyl, aryl,
and heteroaryl organic structures having up to 10 atoms selected
from the group consisting of C, N, and O, and wherein R.sup.3 and
R.sup.4 taken together with the nitrogen to which they are attached
can form a 5 or 6 membered ring containing 0-2 additional
heteroatoms selected from N or O, and wherein R.sup.1 or R.sup.2,
independently, can be attached to R.sup.3 or R.sup.4,
independently, to form a 5 or 6 membered ring containing 0-2
additional heteroatoms selected from N or O, and n is an integer
from 0-10; and an acid selected from the group consisting of
polyphosphoric acid, aminotri(methylene phosphonic acid),
1-hydroxyethylidene-1,1-diphosphonic acid, and 1,2,4-tricarboxylic
acid-butane-2-phosphonic acid.
25. The method claimed in claim 21 wherein the hydroxyamine is
selected from the group consisting of hydroxy-modified
cyclohexylamine, hydroxy-modified morpholine, hydroxy-modified
octadecylamine, N,N-diethylethanolamine,
2-amino-2-methyl-1-propanol, 1,1-dimethylamine-propanol,
2-dimethylamino-2-methyl-1-propanol, hydroxy-modified
N,N-dimethyl-1,3-propanediamine, and ammonium hydroxide.
26. The method claimed in claim 24 wherein the ester has a
hydroxyamine to acid mole ratio in the range of from about 1:1 to
about 3:1.
27. The method claimed in claim 21 further comprising an oxygen
scavenging agent is selected from the group consisting of sulfite
and polyhydroxy acid, wherein the polyhydroxy acid is selected from
the group consisting of ascorbic acid and erythorbic acid.
28. The method claimed in claim 21 further comprising an alkalinity
control agent is selected from the group consisting of carbonate,
hydroxide and amine.
29. The method claimed in claim 21 further comprising a hardness
reducing agent is selected from the group consisting of carbonate,
polyacrylic acid, polymethacrylic acid, and salts thereof, and a
polymaleate; and a glucoheptonate.
30. The method claimed in claim 21 wherein the hydroxyamine is
N,N-diethylethanolamine present in about 0.1% to about 50% by
weight of the composition.
31. The method claimed in claim 21 wherein the ester is
N,N-diethylaminoethanol-1-hydroxyethylene-1-phosphono-1-phosphonate
ester present in about 0.1% to about 50% by weight of the
composition.
32. The method claimed in claim 21 wherein the composition
comprises: Glucoheptonate: 0% to 2.0%; Sulfite: 0.1% to 60%;
Polyhydroxy acid: 0.1% to 5.0%; an ester: 0.01% to 50%; a polymer:
0.1% to 10%; Polymaleate: 0.1% to 10%; Carbonate: 0.0% to 20%;
Water soluble base: 0.0% to 40.0%, wherein the sulfite is selected
from the group consisting of sodium sulfite and potassium sulfite;
the polyhydroxy acid is selected from the group consisting of
ascorbic acid and erythorbic acid; the ester is formed from a
hydroxyamine and a phosphonic acid, wherein the hydroxyamine is
selected from the group consisting of hydroxy-modified
cyclohexylamine, hydroxy-modified morpholine, hydroxy-modified
octadecylamine, N,N-diethylethanolamine,
2-amino-2-methyl-1-propanol, 1,1-dimethylamine-propanol,
2-dimethylamino-2-methyl-1-propanol, hydroxy-modified
N,N-dimethyl-1,3-propanediamine, and ammonium hydroxide, and the
phosphonic acid is selected from the group consisting of
aminotri(methylene phosphonic acid), 1-hydroxyethylidene-1,
1-diphosphonic acid, and 1,2,4-tricarboxylic
acid-butane-2-phosphonic acid, and wherein the polymer is selected
from the group consisting of polyacrylic acid, polymethacrylic
acid, and salts thereof; the polymaleate is polymaleic acid or the
salt thereof; and the carbonate is sodium carbonate or potassium
carbonate.
33. The method claimed in claim 32 wherein the hydroxyamine to
phosphonic acid mole ratio is in the range of from about 1:1 to
about 3:1.
34. The method claimed in claim 32 wherein the ester is
N,N-diethylaminoethanol-1-hydroxyethylene-1-phosphono-1-phosphonate
ester present in about 0.1% to about 50% by weight of the
composition.
35. The method claimed in claim 32 wherein the composition is a
solid.
36. The method claimed in claim 21 wherein the composition
comprises: Sodium Glucoheptonate: 0.01% to 5.0%; Sodium sulfite:
1.0% to 30%; Ascorbic acid: 0.1% to 5.0%; Sodium polymethacrylate
having a molecular weight between 500-5000: 1.0% to 10%;
N,N-diethylaminoethanol-1-hydroxyet- hylene-1-phosphono-1
phosphonate ester: 0.1% to 22.5%; Maleic acid having a molecular
weight between 500-1000: 0.1% to 5.0%; Sodium carbonate: 0% to 20%;
Sodium hydroxide: 0% to 40%; and Water: to 100%, and the
composition is a dry powder.
Description
FIELD OF THE INVENTION
[0001] The invention relates to a method and composition to treat
boiler water. More particularly, the invention relates to a method
of treating boiler water by adding a composition comprising an
ester of a hydroxy amine and an acid in an amount effective to
treat boiler water and related condensate.
BACKGROUND OF THE INVENTION
[0002] A boiler requires extremely pure water in order to avoid a
plurality of different problems. Unfortunately, water coming into
most boilers is not pure enough to avoid these problems. Impurities
in the water, including gases such as oxygen and carbon dioxide,
would rapidly contaminate the water and damage the boiler.
[0003] In addition, condensed steam, referred to as condensate,
generated in the boiler and accompanying boiler lines, is a major
source of impurities. Condensate generally traps impurities,
especially gases including oxygen and carbon dioxide, from the air
and becomes contaminated. The contaminated condensate inevitably
reenters the pool of boiler water, thereby further contaminating
the boiler water. Other problems including accumulation of scale,
maintenance of pH, boiler pitting by oxygen, and the generation of
carbonic acid in the water may occur as a result of contaminated
boiler water. Therefore, the contaminants must be removed or
treated.
[0004] Currently there are a variety of different physical and
chemical treatments for contaminated boiler water. Conventional
treatments have included the use of amines, particularly to
scavenge oxygen and neutralize carbon dioxide. These amines are
generally volatile, having boiling points comparable to elevated
temperatures in the boiler, and vaporize into the steam to treat
the resulting condensate.
[0005] Amines which have been used treat boiler water include
octadecylamine, typically used as a filming amine, and
diethylaminoethanol which has also been used to treat condensate
systems. However, these amines, as well as other conventional
amines commonly used as boiler water treatment agents, typically
are commercially available only as liquids. In addition, the prior
art boiler water treatment compositions containing amines were
prepared and stored as liquids. As with most liquid amines, these
compositions generally emit repugnant and potentially toxic odors
which may be detected during manufacture, packaging, or shipping
processes, and particularly during the use in treating boiler
water. In addition, prolonged storage of liquid amines generally
allows the vapor pressure to build exposing the user to serious
noxious odors and unhealthy levels of vapors. Such amines and
corresponding compositions, therefore, pose possible health and
safety risks to the user and are likely to affect any person
involved with the processing of such boiler treatment agents who
may be exposed to the odors and vapors. Therefore, there exists a
need to relieve the odor generated by liquid amine boiler water
treatment compositions. There also remains a need to improve the
formulation of the amine used to treat boiler water and to improve
the ease and comfort by which the amine may be used to treat boiler
water.
SUMMARY OF THE INVENTION
[0006] The present invention reduces or eliminates amine odors and
corresponding safety risks by providing a method and composition to
treat boiler water by adding an effective amount of an amine which
has been modified in form. Modified amines, such as an ester of a
hydroxyamine, provide effective treatment of boiler water systems
without exposure of the user or processor to repugnant amine odors
and vapors which may threaten health and safety. Modified amines
generally provide a more convenient solid form in which the amine
may be used to treat boiler water.
[0007] Esters of hydroxyamines may be formed by reacting a
hydroxyamine, partially or fully, with an acid. For instance, an
amino-phosphate or phosphonate ester may be formed by reacting a
hydroxyamine with a phosphoric acid or phosphonic acid
respectively. Similarly, amino-sulfate and amino-sulfonate esters
may be formed by reacting a hydroxyamine with a sulfuric acid or a
sulfonic acid respectively. The ester may have a hydroxyamine to
acid mole ratio in the range of from about 1:1 to about 19:1,
preferable greater than about 3:1. Such hydroxyamine-acid ester
mixtures generally reduce or eliminate amine odors and allow the
amine to be added to the boiler water in a solid form for
convenience and comfort of use. Alternatively, the ester may be
combined with other treatment agents which may be added in an
effective amount to treat the boiler water.
[0008] Hydroxyamine-acid esters are effective as boiler water
treatment agents because they generally decompose at elevated
temperatures, such as boiling temperatures, at atmospheric
pressures to a sufficient extent to release effective amounts of
the individual components, i.e., a hydroxyamine and the
corresponding acid. A variety of hydroxyamines, such as
N,N-diethylaminoethanol, 2-amino-2-methyl-1-propanol,
1,1-dimethylamine-propanol, 2-dimethylamino-2-methyl-1-propanol,
and core amines, such as cyclohexylamine, morpholine,
octadecylamine, and N,N-dimethyl-1,3-propanediamine, modified to
include terminal hydroxy groups may be used to form the ester to
treat the boiler water.
[0009] The ester may be formulated into either a liquid or a solid,
as desired, and added directly to treat the boiler water. Both the
liquid and the solid formulations are generally free of odors and
solid compositions may allow easier use and storage. The treatment
composition can generally be provided at high concentrations for
storage and application and is effective at concentrations
determined by the user and dependent on the desired level of
treatment.
[0010] The ester is generally formulated with at least one other
component to form a final treatment composition to effectively
treat boiler water. For instance, the composition may include
additional oxygen scavenging agents, alkalinity control agents,
hardness reducing agents, and iron controlling agents. If the
desired treatment composition is to be formulated as a solid, such
as a dry powder, then each of the other components are generally
mixed in a dry form with the hydroxyamine-acid ester. Effective
quantities of each component may be determined by the user
depending upon the type and level of contamination and desired
treatment concentration. The boiler water treatment composition may
generally be stored and applied at high concentrations or pre-mixed
dilutions which may be added at effective concentrations determined
by the user.
[0011] The present invention will be further appreciated in light
of the following detailed description.
DETAILED DESCRIPTION OF THE INVENTION
[0012] The present invention provides a method of treating boiler
water comprising the addition, to the boiler water, of an effective
amount of hydroxyamine reactant to form an ester. This may be
combined with an oxygen scavenging agent, an alkalinity control
agent, a hardness reducing agent or an iron controlling agent.
[0013] Suitable esters include phosphate esters, phosphonate
esters, sulfate esters, and sulfonate esters. The amine-ester
modification, a reaction between a hydroxyamine and an acid,
typically renders an otherwise potentially pungent amine more
convenient and safe. For example, a phosphate ester of an amine is
generally odorless and has increased viscosity permitting
formulation and packaging of the amino-phosphate ester treatment
reagent as a solid.
[0014] The amine is a hydroxyamine which is modified to form the
ester. The term `modification`, as used herein, refers to a
reaction of a hydroxyamine with an acid to form the corresponding
ester. The term `hydroxyamine`, as used herein, refers to any
primary, secondary or tertiary amine core molecule bearing a
pendant hydroxyl functional group capable of reacting with an acid
to form an ester. Hydroxyamines, suitable for use in the present
invention, may be commercially available from vendors, such as
Aldrich Chemical Company, or privately synthesized as desired to
optimize physical and degradative properties of the
hydroxyamine-acid ester.
[0015] Hydroxyamines can be synthesized by modifying an amine core
molecule to attach the requisite terminal hydroxyl group.
Conventional methods to incorporate a hydroxyl terminus including
conversion of a terminal functional group to a hydroxyl group may
be used. Such methods are disclosed in Advanced Organic Chemistry,
4th Ed. authored by Jerry March, published in 1992. Amine cores
suitable for use in the present invention include octadecylamine,
cyclohexylamine, morpholine, and N,N-dimethyl-1,3-propandiamine.
Core amines which have typically been used to treat boiler water
are generally available commercially as FDA approved liquids.
[0016] Hydroxyamines, suitable for the present invention, have the
general formula: HO--(CR.sup.1R.sup.2).sub.n--N--R.sup.3R.sup.4
wherein R.sup.1 R.sup.2, R.sup.3, and R.sup.4, at each occurrence,
is independently selected from the group consisting of H, alkyl,
cycloalkyl, aryl, and heteroaryl organic substitutions having up to
10 atoms selected from C, N, or O. Substitutions R.sup.1, R.sup.2,
R.sup.3, and R.sup.4, of the general formula above, refer to
organic structures covalently extending from a carbon or nitrogen
atom on the hydroxyamine. The term `alkyl`, as used herein,
generally refers to a straight or branched hydrocarbon chain of
varying length or number of atoms, such as from 1 to 10 atoms. The
term `cyclo alkyl`, as used herein, refers to an unsaturated cyclic
ring comprising carbon, nitrogen, or oxygen atoms in the ring. The
term `aryl`, as used herein, refers to an aromatic ring consisting
of carbon atoms, and the term, `heteroaryl`, as used herein refers
to aromatic rings having heteroatoms, including nitrogen and
oxygen. In addition, these substitutions may bear other functional
groups, such as ethers or amines, which do not participate in the
ester formation.
[0017] The spacer, --(CR.sup.1R.sup.2).sub.n--, between the
hydroxyl group and the amine nitrogen atom, may vary in length,
having `n` atoms ranging from as small as a zero atoms to as long
as 10 atoms. The preferred length is rather small, from 0 to 6
atoms. For example, one embodiment utilizes
2-amino-2-methyl-1-propanol which has a spacer of 2 carbon atoms,
with each of R.sup.1 and R.sup.2 being a methyl group respectively.
Also, ammonium hydroxide, having a 0 atom spacer, is a suitable
hydroxamine for use in the present invention.
[0018] Alternatively, two substitutions may be attached to form
rings. For instance, R.sup.3, and R.sup.4 substitutions, attached
to the hydroxyamine nitrogen, may be joined to form a 5 or 6
membered carbocycle containing 0-2 additional heteroatoms including
nitrogen and oxygen. For example, cyclohexylamine and morpholine
are cyclic amine cores which may be modified to attach a terminal
hydroxyl group from the amine nitrogen atom. Optionally, R.sup.1,
and R.sup.2, independently, may be attached to R.sup.3, or R.sup.4,
independently, to form a 5 or 6 membered carbocyclic ring
containing 0-2 heteroatoms selected from nitrogen and oxygen. For
example, a terminal hydroxyl group may extend from the C3 carbon
atom of a cyclohexylamine core, thus resulting a ring from the
third carbon atom in the spacer to the nitrogen atom on the
hydroxyamine. Suitable hydroxyamines for use in the present
invention include N,N-diethylethanolamine,
2-amino-2-methyl-1-propanol, 1,1-dimethylamine-propanol, and
2-dimethylamino-2-methyl-1-propanol as well as hydroxy modified
amines including hydroxy-modified octadecylamine, hydroxy-modified
cyclohexylamine, hydroxy-modified morpholine, and hydroxy-modified
N,N-dimethyl-1,3-propanediamine.
[0019] A variety of acids, including phosphoric acid, phosphonic
acids, sulfuric acid, sulfonic acids, carboxylic acids, and the
like may be used to form the hydroxyamine-acid ester. For instance,
a phosphoric acid, the general formula (OR).sub.2--P(O)OH, may be
reacted with a hydroxyamine to form an amino-phosphate esteroran
amino-phosphonate ester. Similarly, a hydroxyamine may be reacted
with a sulfuric acid or a sulfonic acid, of the general formula
(OR)S(O).sub.2OH, to form an amino-sulfate ester or an
amino-sulfonate ester respectively. The R groups, independently,
may be H, alkyl, cycloalkyl, aryl or heteroaryl organic structures
having up to 10 atom selected from carbon, nitrogen or oxygen. For
example, substituted phosphoric acids, referred to as phosphonic
acids, such as aminotri(methylene phosphonic acid),
1-hydroxyethylidene-1,1-diphosphonic acid (HEDP), and
1,2,4-tricarboxylic acid-butane-2-phosphonic acid are suitable for
the present invention. The acids may be commercially available or
privately prepared and used to modify the hydroxyamine for use in
treating boiler water.
[0020] Preparation of the hydroxyamine-acid ester may be
accomplished by conventional synthetic methods and generally follow
similar pathways. For example, the preparation of amino-phosphate
esters are described in U.S. Pat. No. 3,477,956 and U.S. Pat. No.
3,528,502. Phosphate esters and phosphonate esters of amines have
traditionally been synthesized through the use of a catalyst, such
as phosphorus pentoxide or other similar catalysts. For example,
typical synthesis have followed the following reaction pathway:
HO--(CR.sup.1R.sup.2).sub.n--N--R.sup.3R.sup.4+(O).dbd.P(OH)(OR.sup.5).sub-
.2+P.sub.2O.sub.5.fwdarw.(O).dbd.P(OR.sup.5).sub.2--O--(CR.sup.1R.sup.2).s-
ub.n--N--R.sup.3R.sup.4
[0021] where each R.sup.5, independently, may be an H as in
phosphoric acid or a substitution, such as an alkyl group discussed
earlier, of a phosphonic acid. The catalyst accelerates the ester
bond formation. The reaction is exothermic in nature and together
with the use of a catalyst, therefore, requires careful control of
the ester formation.
[0022] Amino-phosphate esters used in the present invention may
also be prepared without use of a catalyst. The hydroxyamine is
mixed with a phosphoric acid without the addition of a catalyst.
The reaction pathway follows the general formula:
HO--(CR.sup.1R.sup.2).sub.n--N--R.sup.3R.sup.4+(O).dbd.P(OH)(OR.sup.5).sub-
.2.fwdarw.(O).dbd.P(OR.sup.5).sub.2--O--(CR.sup.1R.sup.2).sub.n--N--R.sup.-
3R.sup.4
[0023] Generally, mixing may comprise adding the hydroxyamine to
the phosphoric acid or vice versa, with the former being preferred.
Typically, the heat generated from the exothermal contact of the
amine with polyphosphoric acid is sufficient to form the ester
linkage. The resulting amino-phosphate ester is generally
vigorously stirred to effect the ester formation. Times required to
form the ester may vary depending upon the desired mole ratio of
the final composition and consequently the weight percentages of
the hydroxyamine and phosphate respectively. Generally, upon
cooling the resulting mixture or slurry is a viscous liquid.
Conventional techniques may then be used to formulate the
amino-phosphate ester for use in the present invention.
[0024] Similarly, sulfate esters and sulfonate esters may be formed
by the same reaction mechanism. Generally, sulfonate esters are
formed by the following reaction pathway:
HO--(CR.sup.1R.sup.2).sub.n--N--R.sup.3R.sup.4+(R.sup.5O)--S(.dbd.O).sub.2-
OH.fwdarw.(R.sup.5O)--S(.dbd.O).sub.2--O--(CR.sup.1R.sup.2).sub.n--N--R.su-
p.3R.sup.4
[0025] where R.sup.5 may be an H as in sulfuric acid or a
substitution, such as an alkyl group discussed earlier, of a
sulfonic acid. Generally, the hydroxyamine is mixed with a sulfuric
acid or a sulfonic acid and vigorously stirred. The reaction may
not be as exothermic in nature as the phosphate ester reaction and
a catalyst or heat, to accelerate the ester bond formation, may be
required. Times required to form the resulting amino-sulfate or
amino sulfonate ester may vary depending upon the desired mole
ratio of the final composition and consequently the weight
percentages of the hydroxyamine and sulfuric acid or sulfonic acid
respectively. Generally, upon cooling the resulting mixture or
slurry is a viscous liquid. Preparation of sulfate esters and
sulfonate esters is further described in Advanced Organic
Chemistry, 4.sup.th Ed. 1992. Conventional techniques may then be
used to formulate the amino-sulfate ester or amino-sulfonate ester
for use in the present invention.
[0026] The hydroxyamine-acid ester may be a mixture generally
containing varying molar ratios of the hydroxyamine to the acid.
Suitable hydroxyamine-acid ester compositions may include
hydroxyamine to acid mole ratios as high as about 19:1. For
example, the hydroxyamine-acid ester may be synthesized by reacting
the hydroxyamine in 95 mole percent with a substituted or
unsubstituted acid, such as phosphoric acid, in about 5.0 mole
percent, to form the hydroxyamine-acid ester mixture having a
hydroxy-amine to acid mole ratio of about 19:1. Similarly, the
hydroxyamine-acid ester may be synthesized by reacting the
hydroxyamine with an acid in equal stoichiometric amounts, or
excess acid, to synthesize a fully esterified hydroxyamine-acid
ester mixture having an amine to acid mole ratio of about 1:1.
Amine odor is reduced significantly as the mole percent of the
hydroxyamine modified to the corresponding hydroxyamine-acid ester
increases. Optimally, a treatment composition comprising the
hydroxyamine-acid ester in a hydroxyamine to acid mole ratio of
about 3:1 has virtually no odor and is sufficiently viscous to be
mixed with dry components to form a solid treatment
composition.
[0027] The hydroxyamine-acid ester composition is effective in
treating boiler water due to its degradative properties. At boiling
temperatures and atmospheric or higher pressures, the
hydroxyamine-acid ester typically breaks down to it's individual
components. The basicity of the treated boiler water, coupled with
hydroxide which may be introduced into the boiler water by the
treatment composition, contributes to the hydrolysis of the
hydroxyamine-acid ester to the corresponding hydroxyamine and
component acid.
[0028] The hydroxyamine-acid ester is preferably added to the
boiler water to result in a hydroxyamine concentration range from
1-200 parts per million in the boiler water and a hydroxyamine
concentration range from 1-200 ppm in the steam. The hydroxyamine
released into the boiler water generally serves to neutralize
carbonic acid and scavenge oxygen in the boiler water and the
corresponding steam. In addition, the degraded component acid, such
as a phosphonic acid, and even the amine-carbonic acid salt, is
generally available to assist in hardness control by metal
chelation and metal transport in the steam boiler.
[0029] The composition may generally be formulated and stored
either as a concentrated aqueous solution or as a solid powder. The
composition may be added to the boiler water directly or as a
solution, by pre-mixing the liquid or solid with water into a
desired concentration, to effect a desired concentration and
desired treatment effect of the boiler water.
[0030] All-in-one treatment compositions may be formulated with the
hydroxyamine-acid ester by the addition of concentrated forms of
multiple components at relative concentrations to allow the
formulated treatment composition to be dispensed into boiler water
and attain the desired use concentrations. The components and the
actual amount of each component added to the concentrated
formulation generally depends on, among other factors, the precise
intended use concentrations and the concentration of each component
as purchased. It will be further appreciated that other carbon
dioxide neutralizing agents may also be added to form the
composition. Examples of additional components which may be used to
formulate the boiler water treatment composition of the present
invention are disclosed and described in U.S. Pat. No. 4,874,541,
and discussed in greater detail below.
[0031] Oxygen scavenging agents are used to scavenge oxygen,
present in the boiler water, to prevent oxygen catalyzed pitting on
the walls and lines in contact with the boiler water. In addition
to the hydroxyamine-acid ester, other oxygen scavengers
conventionally known in the art, may be formulated with the
hydroxyamine-acid ester to form a treatment composition to be added
to the boiler water. For example, sulfites such as sodium or
potassium sulfite and polyhydroxy acids such as ascorbic acid and
erythorbic acid may be used in the composition. The amount of the
oxygen scavenging agent used may vary in accordance with the
desired level of treatment and the amount of oxygen present in the
water. The sulfites, used in the present invention, may generally
be effective if added in the range of about 20 to about 250 parts
per million (ppm) or formulated in the range of 0.1 to 60% by
weight of the composition, while the polyhydroxy acid, may
generally be effective if added in the range of about 1 to about 40
ppm or formulated in the range of about 0.1 to about 5% by weight
of the final composition.
[0032] An alkalinity control agent may be added to the composition
to control the pH, generally a basic pH, in the boiler water.
Conventional alkalinity control agents are suitable for the present
invention including carbonates such as sodium and potassium
carbonate, hydroxides such as ammonium, sodium, or potassium
hydroxide, and amines including various primary, secondary, or
tertiary amines capable of maintaining a basic pH in the water. The
specific amount of the alkalinity control agent used may vary, and
is determined by the user in accordance with factors including
water volume, other acidic or basic components in the water or the
composition, and desired level of treatment. Useful composition
formulations having alkalinity control agents are generally in the
range of 0-70% carbonate and 0-40% hydroxide, by weight of the
composition, as needed to maintain a basic pH in the boiler water.
The amine, such as the hydroxyamines of the present invention, may
effectively scavenge oxygen and maintain a condensate pH in the
range of 7.5 to 8.5, if generally used in a concentration of about
1-200 ppm, preferably in the range of about 25 to about 100 ppm, or
formulated in a range of about 0.01-50% by weight of the final
treatment composition.
[0033] The hardness reducing agents or hydrating compositions
include conventional hardness reducing agents such as carbonates,
including sodium and potassium carbonate, as well as different
types of polymers. Carbonates are typically effective if used in a
concentration of about 20 to about 500 ppm per volume of boiler
water. The polymers, conventionally used to treat hardness in
water, include polyacrylates, such as polymethacrylates, in a
molecular weight range of 500-5000 with the upper molecular
weights, generally around 3000-5000, being preferred. Polyacrylates
may generally be utilized in an amount desired by the user,
however, 1-80 ppm is generally effective, with 12-24 ppm being
preferred. In addition, other polymers such as polymaleates,
generated from polymaleic acid, may also be used to treat hardness.
The polymaleates, used in the present invention, generally will
have a molecular weight between 500-1000 with 750 being preferred.
In addition, the polymaleates may generally be effective if used at
a concentration in the range of 1-80 ppm. The polyacrylates and
polymaleates, used in the present invention, will generally be
effective if formulated in the treatment composition in the range
of 0.01% to about 10% by weight of the composition.
[0034] In addition to the hydroxyamine-acid ester and other
components, the treatment composition may further comprise an iron
controlling agent to control the level of iron in the boiler water.
Conventional agents capable of controlling iron levels in the
boiler water are suitable for the present invention. Generally,
iron controlling agents such as glucoheptonate, i.e., the sodium or
potassium salt thereof, is suitable for the present invention.
Glucoheptonate may be effectively used in a boiler water
concentration range of from about 0 to about 10 ppm or formulated
into a treatment composition in a range of from about 0-2% by
weight of the composition.
[0035] A preferred formulation includes a glucoheptonate, such as
sodium glucoheptonate, present in the composition in a range of
from about 0-2% by weight, a sulfite such as sodium sulfite,
present in the composition in a range of from about 0.1% to about
60% by weight, a polyhydroxy acid, such as ascorbic acid, present
in the composition in a range of from about 0.1% to about 5% by
weight, an amino phosphate ester, such as
N,N-diethylaminoethanol-phosphate ester, present in the composition
in a range of from about 0.1--about 50% by weight, a polymer, such
as a sodium polymethacrylate having a molecular weight between
500-5000 and present in the composition in a range of from about
0.1%--about 10% by weight, a polymaleate composed of maleic acid
having a molecular weight between 500-5000 and present in the
composition in a range of from about 0.1%--about 10% by weight, a
carbonate, such as sodium carbonate, present in the composition in
a range of from about 0%--about 20% by weight, and a water soluble
base, such as sodium hydroxide, present in the composition in a
range of from about 0%--about 40% by weight, with the remaining
weight percent composed of water. An amount of the treatment
composition, effective to treat targeted impurities and to
satisfactorily purify the boiler water, may be added to the boiler.
Generally, about 1000-2000 ppm of the all-in-one treatment
composition is sufficient to treat boilers operating at pressures
below 250 psi, and the composition is dispensed periodically into
the boiler to maintain this concentration in the boiler water.
[0036] Optimal treatment will generally occur with the addition of
a composition comprising sodium glucoheptonate in about 2.64% by
weight, sodium sulfite in about 27.5% by weight, ascorbic acid in
about 2.24% by weight, diethylaminoethanol-HEDP ester in about
16.9% by weight, sodium polymethacrylate in about 5.3% by weight,
sodium polymaleate in about 5.54% by weight, sodium hydroxide in
about 3.87% by weight, sodium tripolyphosphate in about 1.25% by
weight of the composition, and the remaining as water, in a
conventional boiler operating at normal boiler temperatures and
pressures below 250 psi.
[0037] Accordingly, the present invention provides for a method of
treating boiler water by adding an effective amount of a
hydroxyamine-acid ester having a hydroxyamine to acid mole ratio of
at least 1:1. The hydroxyamine-acid ester may be applied as a
concentrated liquid, a dry powder, or as one of many components in
a composition similarly formulated as a concentrated liquid or more
preferably, as a solid, dry powdery form. The hydroxyamine-acid
ester typically lacks the repugnant odor of the un-modified amine
while allowing the amine treatment reagent to be applied and stored
in a form more desirable, safe, and convenient. The
hydroxyamine-acid ester breaks down into its individual components
at boiling temperatures at atmospheric pressure. Therefore,
treatment of boiler water with hydroxyamine-acid esters of the
present invention is as effective as treatment with the amine
reagent itself.
[0038] While the present invention has been illustrated by a
description of various embodiments, and while these embodiments
have been described in detail, it is not the intention of the
applicants to restrict or in any way limit the scope of the
appended claims to such detail. Additional advantages and
modifications will readily appear to those skilled in the art.
Therefore, the invention in its broader aspects is not limited to
the specific details and representative methods as shown and
described. Accordingly, it is apparent that certain modifications
or alterations can be made without departing from the spirit or
scope of the inventor set forth in the appended claims.
* * * * *